EP0584771B2 - Easy to disperse polycarboxylic acid thickeners - Google Patents

Easy to disperse polycarboxylic acid thickeners Download PDF

Info

Publication number
EP0584771B2
EP0584771B2 EP93113458A EP93113458A EP0584771B2 EP 0584771 B2 EP0584771 B2 EP 0584771B2 EP 93113458 A EP93113458 A EP 93113458A EP 93113458 A EP93113458 A EP 93113458A EP 0584771 B2 EP0584771 B2 EP 0584771B2
Authority
EP
European Patent Office
Prior art keywords
interpolymer
weight
anhydride
carboxylic acid
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP93113458A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0584771A1 (en
EP0584771B1 (en
Inventor
Carl Joseph Ii Long
Zahid Amjad
William Frank Masler, Iii
William Howard Wingo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Noveon IP Holdings Corp
Original Assignee
Noveon Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=25467431&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0584771(B2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Noveon Inc filed Critical Noveon Inc
Publication of EP0584771A1 publication Critical patent/EP0584771A1/en
Application granted granted Critical
Publication of EP0584771B1 publication Critical patent/EP0584771B1/en
Publication of EP0584771B2 publication Critical patent/EP0584771B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof

Definitions

  • This invention relates to an interpolymer of olefinically unsaturated carboxylic acids or anhydrides and a polymeric surface active agent (or surfactant), having a linear block or random comb configuration which provides a steric stabilizing component to the interpolymer and produces a polymer which is easier to disperse and handle.
  • Such polymers may be homopolymers of unsaturated polymerizable carboxylic acids, such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid and the like; or copolymers of said acid or anhydride monomers with (meth)acrylate esters, (meth)acrylamides, olefins, maleic anhydrides, vinyl esters, vinyl ethers, and styrenics; or copolymers with other vinyl or vinylidene monomers.
  • copolymers of these acids are cross-linked with small amounts of cross-linking agents.
  • Surfactants have been employed in the manufacture of carboxyl containing polymers because, in their manufacture, the aggregation of the polymer can interfere with the polymerization reaction by retarding access of the monomer to free radicals and by interfering with the removal of the heat produced by the polymerization. Further, the precipitated polymer forms a slurry in the solvent which becomes extremely thick, resulting in ineffective mixing and fouling on reactor surfaces. In response to these problems, and to increase the usually low total solids to a range of about 8 to 17 weight percent and increase productivity, a variety of surfactants have been employed.
  • U.S.-A-4,375,533 to Park et al. discloses a process for overcoming some of the above problems, in which the polymerization of acrylic acid, and optional comonomers, in an organic media, is characterized by the use of nonionic surface active agents having a hydrophobe to lipophobe balance (HLB) values between 1 and about 10.
  • HLB hydrophobe to lipophobe balance
  • U.S.-A-4,420,596, to Lochhead et al. disclosed a process for polymerizing carboxylic acids in mineral spirits, employing nonionic surface active agents having HLB values less than 10.
  • U.S.-A-4,526,937 to Hsu teaches the polymerization of acrylic acid in an organic solvent with a free radical catalyst, using nonionic block copolymers of propylene oxide and ethylene oxide to minimize undesirable flocculation and agglomeration.
  • FR-A-2 270 268 discloses a method for the polymerization of vinyl monomers selected from substituted or unsubstituted styrene, (meth)acrylates, vinylacetates, acrylonitrile or vinylchloride in the presence of a block copolymer of the AB-type, wherein A is the lipophilic and B is the hydrophilic block of the polymer.
  • the present invention resulted from the discovery that in polymerizing olefinically unsaturated carboxylic acid or anhydride monomers containing at least one activated carbon to carbon olefinic double bond and at least one carboxyl group, in an organic media, in the presence of free radical forming catalysts and at least one steric stabilizing polymeric surface active agent (also called surfactant), having at least one hydrophilic moiety and at least one hydrophobic moiety and a linear block or random comb configuration, or mixtures thereof or with other surfactants, an interpolymer, useful as a thickening and emulsifying agent, is produced which is easier to handle and to disperse.
  • the carboxylic acid or anhydride will be at least 15% by weight of the interpolymer.
  • the steric stabilizing surfactant appears to become a part of the polymer molecule by a bonding mechanism or by becoming entangled in the polymer as in an interpenetrating network or by some other force which seems to keep it associated with the polymer molecule.
  • the steric stabilizing surfactant is a molecule of surfactant that has a hydrophilic portion which is associated with the polymer and a hydrophobic portion which extends from the polymer to provide steric stability.
  • the resultant polymer possesses unexpectedly better handling and dispersing characteristics, as well as increased thickening efficiency at lower cross linker concentrations.
  • one is able to obtain an improved interpolymer which is easy to disperse and to handle, and yields lower dispersion viscosities, combined with favorable final application properties such as increased thickening efficiency.
  • This product is achieved using a steric stabilizing surfactant (or steric stabilizer) which becomes associated with the resin in the final product as an interpolymer.
  • the present invention invention relates to the interpolymer of claim 1 and the method of making said interpolymer of claim 18. Preferred embodiments are apparent from the dependent claims.
  • the steric stabilizer may also be used in combination with other surfactants.
  • the amount of steric stabilizing surfactant used in an amount of between 0.01 to 10% is preferred, and 0.2 to 6.0% is further preferred, based upon the weight of the olefinically unsaturated carboxylic acids or anhydrides, to be polymerized.
  • the carboxylic acid or anhydride preferably comprises at least 40% by weight of the interpolymer.
  • Polymerization of the carboxyl-containing monomers, optionally with other vinylidene comonomers, is usually carried out in the presence of a free radical catalyst in a closed vessel in an inert atmosphere under autogenous or artificially-induced pressure, or in an open vessel in an inert atmosphere optionally under reflux at atmospheric pressure.
  • the temperature of the polymerization may be varied from 0° to 125° C or lower or higher.
  • Polymerization at 25° to 90°C using a free radical catalyst is generally effective in providing monomer to polymer conversions of 75 percent to 100 percent.
  • the polymerizations may be either batch, semi-batch or continuous.
  • the agitation may be any agitation sufficient to maintain the slurry and obtain effective heat transfer including, for example, helical agitation, pitched turbines and the like.
  • a useful reaction temperature range is from the range of 20° C to 90° C at 101.3 kPa (1 atmosphere) or more Normal polymerization time is from to 12 hours.
  • Typical free-radical forming catalysts include peroxygen compounds such as sodium, potassium and ammonium persulfates, caprylyl peroxide, benzoyl peroxide, hydrogen peroxide, pelargonyl peroxide, cumene hydroperoxides, diisopropyl peroxydicarbonate, tertiary butyl diperphthalate, tertiary butyl perbenzoate, sodium peracetate and di-(2-ethylhexyl) peroxy dicarbonate, as well as azo catalysts such as azobis(isobutyronitrile).
  • Other catalysts utilizable are the so-called "redox' type of catalyst and the heavy-metal activated catalyst systems.
  • Ultraviolet light may also be used to generate free radicals. Some systems polymerize solely by heat, but catalysts generally provide better control. The monomers may be batch charged or continuously added during the course of polymerization or by any other manner of polymerization techniques conventionally used.
  • the medium used for the polymerization is an organic fluid, or mixtures of organic fluids, in which the monomers are preferably soluble but in which the polymer is substantially insoluble, so that the polymer product is preferably obtained as a fine friable or fluffy precipitate.
  • the organic media is selected from the group consisting of hydrocarbons containing 6 to 40 carbon atoms, halocarbons, chlorofluoroalkanes, esters, and ketones.
  • Typical monomer solvents include liquid hydrocarbons selected from alkanes of 5 to 10, preferably 6 to 8 carbon atoms, such as hexane and heptane; cycloalkanes of 4 to 8, preferably 5 to 7 carbon atoms, such as cyclohexane; benzene and alkyl-substituted benzenes containing 1 to 2 lower alkyl substituents, preferably methyl substituents, such as toluene and xylene; alkyl carboxylates containing 1 to 6 preferably 1 to 4 carbon atoms in the alkyl groups and 2 to 6, preferably 2 to 4 carbon atoms in the carboxylate moiety, such as ethyl acetate, isopropyl acetate, propyl acetate, methyl acetate, and butyl acetate; haloalkanes and chlorofluoroalkanes, containing 1 to 3 carbon atoms and at least 2 halo groups,
  • Such polymers are homopolymers of an unsaturated, polymerizable carboxylic monomers such as acrylic acid, methacrylic acid, maleic acid, itaconic acid and maleic anhydride, and copolymers of polymerizable carboxylic monomers with acrylate esters, acrylamides, olefins, vinyl esters, vinyl ethers, or styrenics.
  • the carboxyl containing polymers have molecular weights greater than 500 to as high as several million, usually greater than 10,000 to 900,000 or more.
  • Copolymers include copolymers of acrylic acid with small amounts of polyalkenyl polyether cross-linkers that are gel-like polymers, which, especially in the form of their safts, absorb large quantities of water or solvents with subsequent substantial increase in volume.
  • Carboxylic polymers and copolymers such as those of acrylic acid and methacrylic acid also may be cross-linked with polyfunctional materials as divinyl benzene and unsaturated diesters as is disclosed in U.S. -A-2,340,110 ; 2,340,111 ; and 2,533,635 .
  • Olefinically-unsaturated acids of this class include such materials as the acrylic acids typified by the acrylic acid itself, alpha-cyano acrylic acid, beta methylacrylic acid (crotonic acid), alpha-phenyl acrylic acid, beta-acryloxy propionic acid, cinnamic acid, p-chloro cinnamic acid, 1-carboxy-4-phenyl butadiene-1,3, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, maleic acid, fumaric acid, and tricarboxy eth lene.
  • acrylic acids typified by the acrylic acid itself, alpha-cyano acrylic acid, beta methylacrylic acid (crotonic acid), alpha-phenyl acrylic acid, beta-acryloxy propionic acid, cinnamic acid, p-chloro cinnamic acid, 1-carboxy-4-phenyl butadiene-1,3, itaconic acid, cit
  • carboxylic acid includes the polycarboxylic acids and those acid anhydrides, such as maleic anhydride, wherein the anhydride group is formed by the elimination of one molecule of water from two carboxyl groups located on the same carboxylic acid molecule.
  • R and R' are selected from the group consisting of hydrogen, halogen and cyanogen (-C ⁇ N) groups and alkyl, aryl, alkaryl, aralkyl, and cycloalkyl groups such as methyl, ethyl, propyl, octyl, decyl, phenyl, tolyl, xylyl, benzyl and cyclohexyl.
  • the preferred carboxylic monomers are the monoolefinic acrylic acids having the general structure wherein R 2 is a substituent selected from the class consisting of hydrogen, halogen, and the cyanogen (-C ⁇ N) groups, monovalent alkyl radicals, monovalent aryl radicals, monovalent aralkyl radicals, monovalent alkaryl radicals and monovalent cycloaliphatic radicals. Of this class, acrylic and methacrylic acid are most preferred. Other useful carboxylic monomers are maleic acid and its anhydride.
  • the polymers include both homopolymers of carboxylic acids or anhydrides thereof, or the defined carboxylic acids copolymerized with one or more other vinylidene monomers containing at least one terminal >CH 2 group.
  • the other vinylidene monomers are present in an amount of less than 30 weight percent based upon the weight of the carboxylic acid or anhydride plus the vinylidene monomer(s).
  • Such monomers include, for example, acrylate ester monomers including those acrylic acid ester monomers such as derivatives of an acrylic acid represented by the formula wherein R 3 is an alkyl group having from 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms and R 2 is hydrogen, methyl or ethyl, present in the copolymer in amount, for example, from 1 to 40 weight percent or more.
  • acrylate ester monomers including those acrylic acid ester monomers such as derivatives of an acrylic acid represented by the formula wherein R 3 is an alkyl group having from 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms and R 2 is hydrogen, methyl or ethyl, present in the copolymer in amount, for example, from 1 to 40 weight percent or more.
  • acrylates include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, methyl methacrylate, methyl ethacrylate, ethyl methacrylate, octyl acrylate, heptyl acrylate, octyl methacrylate, isopropyl methacrylate, 2-ethylhexyl methacrylate, nonyl acrylate, hexyl acrylate and n-hexyl methacrylate.
  • Higher alkyl acrylic esters are decyl acrylate, isodecyl methacrylate, lauryl acrylate, stearyl acrylate, behenyl acrylate and melissyl acrylate. Mixtures of two or three or more long chain acrylic esters may be successfully polymerized with one of the carboxylic monomers.
  • Other comonomers include olefins, including alpha olefins, vinyl ethers, vinyl esters, and mixtures thereof.
  • Cross-linking monomers for use in preparing the copolymers are polyalkenyl polyethers having more than one alkenyl ether grouping per molecule. They are made by the etherification of a polyhydric alcohol containing at least 2 carbon atoms and at least 2 hydroxyl groups. Compounds of this class may be produced by reacting an alkenyl halide, such as allyl chloride or allyl bromide, with a strongly alkaline aqueous solution of one or more polyhydric alcohols. The product may be a complex mixture of polyethers with varying numbers of ether groups. Analysis reveals the average number of ether groupings on each molecule.
  • Efficiency of the polyether cross-linking agent increases with the number of potentially polymerizable groups on the molecule. It is preferred to utilize polyethers containing an average of two or more alkenyl ether groupings per molecule. Typical agents are allyl pentaerythritol, allyl sucrose, and trimethylolpropane diallyl ether.
  • the polymeric mixtures contain 0.01 to 5% by weight of cross-linking monomer based on the total of carboxylic acid monomer, plus other monomers, if present, and more preferably 0.01 to 3.0 weight percent.
  • vinylidene monomers may also be used, including the acrylic nitrites.
  • the useful ⁇ , ⁇ -olefinically unsaturated nitriles are preferably the monoolefinically unsaturated nitriles having from 3 to 10 carbon atoms such as acrylonitrile and methacrylonitrile. Most preferred are acrylonitrile and methacrylonitrile.
  • the amounts used are, for example, for some polymers are from 1 to 30 weight percent of the total monomers copolymerized.
  • Acrylic amides containing from 3 to 35 carbon atoms including monoolefinically unsaturated amides also may be used.
  • amides include acrylamide, methacrylamide, N-t-butyl acrylamide, N-cyclohexyl acrylamide, higher alkyl amides, where the alkyl group on the nitrogen contains from 8 to 32 carbon atoms, acrylic amides including N-alkylol amides of alpha,beta-olefinically unsaturated carboxylic acids including those having from 4 to 10 carbon atoms such as N-methylol acrylamide, N-propanol acrylamide, N-methylol methacrylamide, N-methylol maleimide, N-methylol maleamic acid esters and N-methylol-p-vinyl benzamide.
  • Still further useful materials are alpha-olefins containing from 2 to 30 carbon atoms, preferably 2 to 18 and more preferably from 2 to 8 carbon atoms; dienes containing from 4 to 10 carbon atoms; vinyl esters and allyl esters such as vinyl acetate; vinyl aromatics such as styrene, methyl styrene and chlorostyrene; C 1 -C 5 alkyl vinyl ethers and allyl ethers and ketones such as vinyl methyl ether and methyl vinyl ketone; chloroacrylates; cyanoalkyl acrylates such as ⁇ -cyanomethyl acrylate, and the ⁇ -, ⁇ -, and ⁇ -yanopropyl acrylates; alkoxyacrylates such as methoxy ethyl acrylate; haloacrylates as chloroethyl acrylate; vinyl halides and vinyl chloride and vinylidene chloride; divinyls, diacrylates and other polyfunctional monomers such as divin
  • the steric stabilizer functions to provide a steric barrier which repulses approaching particles.
  • a requirement for the steric stabilizer is that a segment of the dispersant (i.e., a hydrophobe) be very soluble in the solvent (the continuous phase in a nonaqueous dispersion polymerization process) and that another segment (i.e., a hydrophile) be at least strongly adhered to the growing polymer particle.
  • the steric stabilizers of the present invention have a hydrophilic group and a hydrophobic group.
  • the steric stabilizers are block copolymers comprising a soluble block and an anchor block having a molecular weight (i,e., chain length) usually well above 1000, but a hydrophobe length of more than 5 nm (50 Angstroms), as calculated by the Law of Cosines. These dimensions are determined on the extended configuration using literature values for bond lengths and angles.
  • the steric stabilizers of the present invention are distinguishable from the prior art steric surfactants which may be block copolymers, but have hydrophobe lengths of less than 5 nm (50 Angstroms).
  • the steric stabilizer of the present invention has either a linear block or a comb configuration, and has a hydrophobe of sufficient length to provide a sufficient steric barrier.
  • the steric stabilizer is a linear block copolymeric steric stabilizer, it is defined as mentioned above.
  • hydrophilic groups are polyethylene oxide, poly(1,3-dioxolane), copolymers of polyethylene oxide or poly(1,3-dioxolane), poly(2-methyl-2-oxazoline polyglycidyl trimethyl ammonium chloride and polymethylene oxide, with polyethylene oxide being preferred.
  • hydrophobic groups are polyesters, such as those derived from 2-hydroxybutyric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxycaproic acid, 10-hydroxydecanoic acid, 12-hydroxydodecanoic acid, 16-hydroxyhexadecanoic acid, 2-hydroxyisobutyric acid, 2-(4-hydroxyphenoxy) propionic acid, 4-hydroxyphenylpyruvic acid, 12-hydroxystearic acid, 2-hydroxyvaleric acid, polylactones, such as caprolactone, butyrolactone, polylactams, such as those derived from caprolactam, polyurethanes, polyisobutylene, where the hydrophobe should provide a steric barrier of greater than 5 nm (50 Angstoms), preferably greater than 7.5 nm (75 Angstroms), with greater than 10 nm (100 Angstroms) being also preferred, with polyhydroxy fatty acids, such as poly(12-hydroxystearic acid) being preferred.
  • the steric barrier
  • Steric stabilizer molecules comprise both hydrophilic and hydrophobic units.
  • Hydrophobic polymer units or hydrophobic blocks may be prepared by a number of well known methods. These methods include condensation reactions of hydroxy acids, condensation of polyols (preferably diols) with polycarboxylic acids (preferably diacids).Other useful methods include polymerization of lactones and lactams, and reactions of polyols with polyisocyanates. Hydrophobic blocks or polymer units can be reacted with hydrophilic units by such reactions as are known to those skilled in the art. These reactions include condensation reactions and coupling reactions, for example. Subsequent to the steric stabilizer preparation, the stabilizers may be further reacted with modifying agents to enhance their utility. U.S.-A-4,203,877 to Alan S. Baker teaches making such steric stabilizers, and the entire disclosure thereof is incorporated herein by reference.
  • the steric stabilizer is a random copolymeric comb steric stabilizer, it is defined as mentioned above.
  • hydrophobic monomer unit or moiety examples include dimethyl siloxane, diphenyl siloxane, methylphenyl siloxane, alkyl acrylate and alkyl methacrylate, with dimethyl siloxane being preferred.
  • hydrophilic monomer unit or moiety examples include methyl-3-polyethoxypropyl siloxane-n-phosphate or sulfate, and the alkali metal or ammonium salts derived therefrom; units derived from polyethoxy (meth)acrylate containing from 1 to 40 moles of ethylene oxide; acrylic acid; acrylamide-, methacrylic acid, maleic anhydride; dimethyl amino ethyl (meth)acrylate; or its salts with methyl chloride or dimethyl sulfate; dimethyl amino propyl(meth)acrylamide and its salts with methyl chloride or dimethyl sulfate, with methyl-3-polyethoxypropyl siloxane- ⁇ -phosphate being preferred.
  • terminating agents are monohalo silanes, mercaptans, haloalkanes, alkyl aromatics and alcohols, which will produce terminating groups such as trialkyl silyl, alkyl, aryl alkyl and alcoholate, with the preferred terminating groups being trimethyl silyl.
  • a random copolymeric comb steric stabilizer is a dimethicone copolyol phosphate which has the following formula: where x and y are integers greater than 1, and z is an integer from 1 to 100.
  • Such a copolymeric comb steric stabilizer is available commercially under the trade name Pecosil® from Phoenix Chemical, Somerville, New Jersey
  • the steric stabilizers of the appropriate structure in accordance with the present invention have the potential for becoming part of a (meth)acrylic acid or anhydride-containing polymer as an interpolymer by several mechanisms, including a bonding mechanism. These would include graft-type polymerization, hydrogen bonding, olefinic unsaturation polymerization, or condensation reaction. While we do not wish to be bound by a particular bonding mechanism theory, its explanation is felt to be helpful in understanding the invention.
  • the polyethylene oxide segment which is known to hydrogen bond strongly to polycarboxylic acids, will react with the polycarboxylic acid and result in the formation of a hydrogen bonded complex.
  • longer polyethylene oxide segments will give more strongly-bonded complexes.
  • Another possible bonding mechanism is the polymerization of olefinic unsaturation in the stabilizer with the growing polymer chain.
  • Some stabilizers contain a certain degree of unsaturation and this unsaturation may react via the following general pathway:
  • a polymerization reaction was conducted in a water jacketed two liter Pyrex resin kettle equipped with mechanical stirrer, a thermometer and reflux condenser topped with a nitrogen inlet connected to a bubbler to provide a slightly positive pressure of nitrogen throughout the polymerization.
  • the water jacket was connected to a constant temperature circulator.
  • the resin kettle was charged with ethyl acetate (688.5 grams), cyclohexane (586.5 grams), acrylic acid (218.25 grams), stearyl methacrylate (6.75 grams), allylpentaerythritol (1.35 grams), and a steric stabilizing surface active agent in accordance with the present invention in a varied amount based upon the weight of the acrylic acid and co-acrylate ester monomers (i.e., phm or parts per hundred monomers).
  • AA interpolymer In making an acrylic acid interpolymer (hereinafter also referred to as AA interpolymer), no stearyl methacrylate was used, the amount of acrylic acid was 225 grams, the amount of allylpentaerythritol was 2.25 grams, and the amount of steric stabilizer was based upon the amount of acrylic acid monomer solids. In either case, the mixture was sparged with nitrogen for 30 minutes while the reactor was heated to 50°C, At 50°C, the sparging tube was removed while a nitrogen purge was maintained, stirring was begun, and the recipe amount of di-(2-ethylhexyl)-peroxydicarbonate (in an amount of 0.275 to 0.98 grams) was added.
  • Dispersion times were done using a 1% dispersion (4 g resin/396 g water) prepared in demineralized (DM) water, using a Servodyne mixer (Cole Parmer) with an S-paddle at 400 rpm.
  • the resin was introduced through a 0.84 mm (20 mesh) screen, with stirring.
  • the speed of hydration was visually assessed by the transparency of the wetted swollen microgels. The more transparent the microgel particle appears to be, the faster is the speed of hydration.
  • the powder was considered not to be “easy to disperse”. Typically, if the product was dusty, i.e., fine, it was also not was easy to disperse.
  • a clarity measurement is the percentage of light transmitted through the dispersed, hydrated and neutralized polymer at a resin concentration of 0.5%. Clarity is measured with a Brinkman PC 801 colorimeter at 420 nanometers (nm). The higher the percent transmittance, the better the clarity A transmittance of greater than 60% is acceptable.
  • a 1% stock dispersion of resin or interpolymer (8 g resin/792 g water) was prepared in demineralized (DM) water, using a Lightnin' mixer at 1,000 rpm with a 3-blade marine impeller. The resin was introduced through a 0.84mm (20 mesh) screen with stirring and the dispersion was mixed for a total of one hour.
  • the viscosity of the dispersion is referred to as the Dispersion Viscosity or Un-neutralized Viscosity.
  • Dispersions can also be made with 2.5% resin, in which case the amounts are adjusted proportionately.
  • An easy to disperse and easy to handle polymer will have a low dispersion time, in terms of minutes to disperse, while also having a relatively low dispersion (i.e., Un-neutralized) Viscosity.
  • Un-neutralized dispersion Viscosity
  • resin at 1 % resin an Un-neutralized Dispersion Viscosity of less than 1000 mPa ⁇ s [centipoise (cPs)] would be desirable, while at 2.5% resin an Un-neutralized Viscosity of less than 6000 mPa ⁇ s (cPs) is desirable.
  • the 1% stock dispersion was then used to make the following typical concentrations for analysis, some or all of which may be measured: 0.2% Mucilage (80 g of stock dispersion diluted to a total of 400 g with DM water) 0.5% Mucilage (200 g of stock dispersion diluted to a total of 400 g with DM water) 1.0% Mucilage (400 g of stock dispersion used as is)
  • the samples were then measured for pH and Brookfield Viscosity using a Brookfield RVT-DV Viscometer at 20 rpm.
  • the viscosity of the neutralized dispersions is referred to as the Neutralized Viscosity.
  • a Neutralized Viscosity of more than 20,000 mPa ⁇ s (cPs) at 0.5% resin concentration is desirable.
  • Salt sensitivity on 1.0% mucilages are evaluated at 1.0% salt concentrations in the following manner:
  • an interpolymer made from comonomers, incorporating a steric stabilizer in accordance with the present invention, is easier to disperse while retaining good ultimate thickening properties.
  • the dispersion times for the Un-neutralized Dispersions are less than 15 minutes when compared to 75 minutes for the control resin (i.e., no steric stabilizer), and the interpolymers generally achieve less than 1000 mPa ⁇ s (cPs) un-neutralized viscosities.
  • the neutralized resins have viscosities of greater than 20,000 mPa ⁇ s (cPs), and the interpolymers show good salt sensitivity.
  • interpolymers can be produced under varying amounts of steric stabilizer and/or varying amounts of crosslinker
  • polymers were prepared in accordance with the typical co-interpolymer reaction, using Hypermer® B-239 surfactant as the steric stabilizer.
  • the amount of crosslinker i.e., allylpentaerythritol
  • the steric stabilizer was varied in an amount of between 0.25% and 5.0% by weight based upon the weight of the monomer (parts per hundred weight of monomer or phm) while the amount of crosslinker was held constant (Examples 18-25).
  • the polymerization solids, the vinylic monomers, i.e., the amount of acrylic acid plus co-acrylate ester monomer solids was 15% by weight based upon the total weight of the vinylic monomers plus the polymerization solvent.
  • Crosslinker Steric Stabilizer dose Neutralized Viscosity 1% Salt Sensitivity Viscosity (mPa ⁇ s) (phm) (phm) (mPa ⁇ s) 1.0% Resin 12 0.2 1.0 4,020 7,600 13 0.4 1.0 11,400 7,800 14 0.6 1.0 31,000 8,250 15 0.8 1.0 67,000 7,450 16 1.0 1.0 109,000 5,200 17 1.2 1.0 137,000 3,300 18 0.6 0.25 34,600 7,900 19 0.6 0.50 38,000 8,650 20 0.6 0.75 34,800 8,200 21 0.6 1.0 31,000 8,250 22 0.6 1.5 36,000 7,950 23 0.6 2.0 39,200 7,700 24 0.6 3.0 43,400 7,250 25 0.6 5.0 50,000 6,850
  • the samples consist of a control (i.e., without steric stabilizing surfactant), along with the four samples prepared with 5% by weight, based upon the weight of the acrylic acid monomers, of a steric stabilizer, namely, Hypermer® B-239, B-246, or B-261 surfactant, added to the monomer premix prior to initiation of the polymerization and a "post-add" control sample in which a control sample was reslurried in cosolvent and 5% steric stabilizer (Hypermer® B-261 surfactant) was added (i.e., post added) to the slurry which was then dried.
  • a control i.e., without steric stabilizing surfactant
  • a steric stabilizer namely, Hypermer® B-239, B-246, or B-261 surfactant
  • the use of a steric stabilizer has little effect on weight average molecular weight (Mw) of the polymer.
  • Mw weight average molecular weight
  • the ability to extract the steric stabilizer decreases as the molecular weight of the steric stabilizer increases, presumably due to interpolymer chain entanglements.
  • This can be corroborated by the fact that it is possible to extract nearly twice as much of the Hypermer® B-261 surfactant out of the post added sample of polyacrylic acid as in the pretreatment case.
  • the fact that not all the Hypermer® B-261 surfactant in the post add case is extractable is explained by the high affinity for hydrogen bonding between the polyethylene oxide blocks in the steric stabilizers and the carboxylic acids on the surface of the resin particles.
  • the strength of the hydrogen bonded complex will be related to the relative length of the polyethylene oxide block, the greater the number of hydrogen bonded sites, the stronger the complex.
  • the molecular weight data on the steric stabilizers also substantiates the molecular weight dependency on extractability.
  • the molecular weight data is very close between the pure and extracted samples, indicating a uniform extraction.
  • the extracted molecular weight is significantly lower than the pure material, with the Hypermer® B-261 surfactant being the lowest. This shows a definite bias for the extractability of the low molecular weight fractions in the steric stabilizers.
  • Vazo® 67 which is azobis(2-methyl butyronitrile), and available from the E.I. du Pont de Nemours & Company, Inc. was substituted for the di-(2-ethylhexyl)-peroxydicarbonate used in the typical copolymer reaction and an inter-polymer was produced that had a neutralized viscosity of 80,000 mPa ⁇ s (cPs) at 1.0% resin concentration and a clarity of 89%, which are desirable end thickening properties.
  • cPs mPa ⁇ s
  • cyclohexane was employed as the solvent in accordance with the typical co-interpolymer reaction, at crosslinker levels of 0.6 and 0.8 parts per hundred vinylic monomer (phm) and 12% total solids using Hypermer® 2234 surfactant at a dose of 4.0 phm, and an interpolymer was produced which achieved dispersion viscosities of 320 and 15 mPa ⁇ s (cPs) at 2.5% resin concentration, 11,000 and 37,000 mPa ⁇ s (cPs) neutralized viscosity at 0.5% resin concentration, and clarity of 88 and 48%, respectively.
  • Example A was repeated using a different cut of mineral spirits, namely, one having a flash point of 79.4°C (175°F)
  • the resulting polymer at a 0.5% mucilage, had a neutralized viscosity of 43,500 mPa ⁇ s (cPs) which demonstrates that the same results can be achieved using different solvents.
  • the reaction mixture was sparged with dry nitrogen for 15 minutes at room temperature and then the reaction mixture was heated to 72°C with sparging for an additional 15 minutes.
  • PEG polyethylene glycol
  • PEG ethers Brij® brand surfactants
  • Triton® brand surfactants PEG diesters
  • PEG polysorbate esters Teween surfactants
  • fatty acid partial esters of sorbitan Span® surfactants
  • ethylene oxide block copolymers Pluronic® brand surfactants
  • this invention claims an interpolymer which by utilizing a steric stabilizing surfactant in the polymerization of the resin is easy to disperse and/or has increased efficiency. These resins disperse in minutes when added to water, yield lower un-neutralized dispersion viscosities and have no detrimental effects on final application properties.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Detergent Compositions (AREA)
EP93113458A 1992-08-26 1993-08-24 Easy to disperse polycarboxylic acid thickeners Expired - Lifetime EP0584771B2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US935616 1992-08-26
US07/935,616 US5288814A (en) 1992-08-26 1992-08-26 Easy to disperse polycarboxylic acid thickeners

Publications (3)

Publication Number Publication Date
EP0584771A1 EP0584771A1 (en) 1994-03-02
EP0584771B1 EP0584771B1 (en) 1997-12-29
EP0584771B2 true EP0584771B2 (en) 2008-05-07

Family

ID=25467431

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93113458A Expired - Lifetime EP0584771B2 (en) 1992-08-26 1993-08-24 Easy to disperse polycarboxylic acid thickeners

Country Status (16)

Country Link
US (4) US5288814A (zh)
EP (1) EP0584771B2 (zh)
JP (1) JP3273089B2 (zh)
KR (1) KR100294936B1 (zh)
CN (1) CN1051094C (zh)
AT (1) ATE161553T1 (zh)
AU (1) AU676841B2 (zh)
BR (1) BR9303434A (zh)
CA (1) CA2104835A1 (zh)
DE (1) DE69315910T2 (zh)
ES (1) ES2111673T5 (zh)
IL (1) IL106724A (zh)
MX (1) MX183685B (zh)
MY (2) MY132334A (zh)
TW (1) TW260676B (zh)
ZA (1) ZA936157B (zh)

Families Citing this family (158)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5382381A (en) * 1992-12-14 1995-01-17 John Imperante Alkoxylated silicone phosphate esters as emulsifiers
US5830967A (en) * 1994-10-24 1998-11-03 Amcol International Corporation Process for producing an oil and water adsorbent polymer capable of entrapping solid particles and liquids and the product thereof
US5608005A (en) * 1994-10-24 1997-03-04 Amcol International Corporation Process for viscosifying water with carboxylic acid monomers polymerized in silicone solvents
US5618877A (en) * 1994-10-24 1997-04-08 Amcol International Corporation Process for polymerization of water-soluble and water-insoluble carboxylic acid polymers and copolymers in a silicone oil solvent
US5837790A (en) 1994-10-24 1998-11-17 Amcol International Corporation Precipitation polymerization process for producing an oil adsorbent polymer capable of entrapping solid particles and liquids and the product thereof
US6107429A (en) * 1994-10-24 2000-08-22 Amcol International Corporation Process for producing an oil and water adsorbent polymer capable of entrapping solid particles and liquids and the product thereof
IT1270705B (it) 1994-11-17 1997-05-07 3V Sigma Spa Composizioni addensanti.
US5712358A (en) * 1995-06-07 1998-01-27 Amcol International Corporation Process for producing an oil sorbent copolymer and the product thereof
DE19600324A1 (de) 1996-01-08 1997-07-10 Basf Ag Granulate für kosmetische und pharmazeutische Zubereitungen
US6028016A (en) * 1996-09-04 2000-02-22 Kimberly-Clark Worldwide, Inc. Nonwoven Fabric Substrates Having a Durable Treatment
US6296936B1 (en) 1996-09-04 2001-10-02 Kimberly-Clark Worldwide, Inc. Coform material having improved fluid handling and method for producing
US6060636A (en) * 1996-09-04 2000-05-09 Kimberly-Clark Worldwide, Inc. Treatment of materials to improve handling of viscoelastic fluids
US6017832A (en) * 1996-09-04 2000-01-25 Kimberly-Clark Worldwide, Inc. Method and composition for treating substrates for wettability
US6204208B1 (en) 1996-09-04 2001-03-20 Kimberly-Clark Worldwide, Inc. Method and composition for treating substrates for wettability and skin wellness
US5750047A (en) * 1997-03-13 1998-05-12 The B.F. Goodrich Company Anti-icing fluids
US5997764A (en) * 1997-12-04 1999-12-07 The B.F. Goodrich Company Thickened bleach compositions
CA2313686C (en) * 1997-12-12 2011-02-22 Caterpillar Inc. Constant heating value aqueous fuel mixture and method for formulating the same
US6492488B1 (en) 1998-08-02 2002-12-10 Pmd Holdings Corp. Controlled release polyacrylic acid granules and a process for preparing the same
US6211296B1 (en) 1998-11-05 2001-04-03 The B. F. Goodrich Company Hydrogels containing substances
US6262207B1 (en) * 1998-12-18 2001-07-17 3M Innovative Properties Company ABN dispersants for hydrophobic particles in water-based systems
US6361768B1 (en) 1998-12-29 2002-03-26 Pmd Holdings Corp. Hydrophilic ampholytic polymer
GB9903140D0 (en) 1999-02-12 1999-04-07 Basf Ag Interpolymers
US6297337B1 (en) 1999-05-19 2001-10-02 Pmd Holdings Corp. Bioadhesive polymer compositions
JP2000355614A (ja) * 1999-06-15 2000-12-26 Sumitomo Seika Chem Co Ltd カルボキシル基含有重合体組成物
US6623756B1 (en) * 2000-04-27 2003-09-23 Noveon Ip Holdings Corp. Directly compressed solid dosage articles
US6410005B1 (en) 2000-06-15 2002-06-25 Pmd Holdings Corp. Branched/block copolymers for treatment of keratinous substrates
MY128134A (en) * 2000-09-28 2007-01-31 Novartis Ag Compositions and methods for cleaning contact lenses
US6433061B1 (en) 2000-10-24 2002-08-13 Noveon Ip Holdings Corp. Rheology modifying copolymer composition
JP4782940B2 (ja) * 2001-04-27 2011-09-28 株式会社日本触媒 親水性グラフト重合体の製造方法
US6623754B2 (en) 2001-05-21 2003-09-23 Noveon Ip Holdings Corp. Dosage form of N-acetyl cysteine
US7250448B2 (en) 2001-12-07 2007-07-31 Hercules Incorporated Anionic copolymers prepared in an inverse emulsion matrix and their use in preparing cellulosic fiber compositions
ES2687970T3 (es) 2002-09-05 2018-10-30 Vanderbilt Royalty Sub L.P. Composiciones y kits para la eliminación de compuestos irritantes de las superficies corporales
GB2393908A (en) * 2002-10-12 2004-04-14 Reckitt Benckiser Inc Thickened, abrasive containing, liquid disinfectant
US7396874B2 (en) 2002-12-06 2008-07-08 Hercules Incorporated Cationic or amphoteric copolymers prepared in an inverse emulsion matrix and their use in preparing cellulosic fiber compositions
KR100508570B1 (ko) * 2003-04-07 2005-08-17 주식회사 엘지화학 전극 활물질 슬러리 제조시의 분산제 조성 및 그 이용
NL1023720C2 (nl) * 2003-06-23 2004-12-28 Univ Eindhoven Tech Werkwijze voor het wijzigen van de transporteigenschappen van een materiaal, werkwijze voor het vrijmaken van een werkstof uit een implantaat, evenals implantaat met werkstof.
FR2856691B1 (fr) * 2003-06-26 2005-08-26 Seppic Sa Nouveau polymere en poudre, procede pour sa preparation et utilisation comme epaississant
WO2005028550A2 (en) * 2003-07-09 2005-03-31 Virginia Commonwealth University Method for polymeric surface modification
US7098180B2 (en) * 2003-08-28 2006-08-29 Johnson & Johnson Consumer Companies Inc. Mild and effective cleansing compositions
US7119059B2 (en) * 2003-08-28 2006-10-10 Johnson & Johnson Consumer Companies, Inc. Mild and effective cleansing compositions
US20050070452A1 (en) * 2003-08-28 2005-03-31 Joseph Librizzi Methods of reducing irritation in personal care compositions
US7084104B2 (en) * 2003-08-28 2006-08-01 Johnson & Johnson Consumer Company Inc. Mild and effective cleansing compositions
US7157414B2 (en) * 2003-08-28 2007-01-02 J&J Consumer Companies, Inc. Methods of reducing irritation in personal care compositions
US20050075256A1 (en) * 2003-08-28 2005-04-07 Joseph Librizzi Methods of reducing irritation associated with personal care compositions
US20050049172A1 (en) * 2003-08-28 2005-03-03 Lukenbach Elvin R. Mild and effective cleansing compositions
US20050137110A1 (en) 2003-12-17 2005-06-23 Scott Douglas C. Compositions and methods of delivering bleaching agents to teeth
US7473739B2 (en) * 2004-02-05 2009-01-06 Nippon Shokubai Co., Ltd. Particulate water absorbent agent and production method thereof, and water absorbent article
US20060135383A1 (en) * 2004-12-17 2006-06-22 Cossa Anthony J Cleansing compositions comprising polymeric emulsifiers and methods of using same
BRPI0607038A2 (pt) * 2005-01-28 2009-12-01 Basf Ag uso de polìmeros composições cosméticas para cabelo, e para pele, e, composição dermatólogica
WO2006107723A1 (en) * 2005-04-01 2006-10-12 Neurogesx, Inc. Oils of capsaicinoids and methods of making and using the same
TWI353360B (en) 2005-04-07 2011-12-01 Nippon Catalytic Chem Ind Production process of polyacrylic acid (salt) wate
CN101247854B (zh) * 2005-05-10 2012-03-21 强生消费者公司 低刺激性组合物及其制备方法
CN101237851B (zh) * 2005-06-16 2013-09-18 沃纳奇尔科特有限责任公司 用于阴道给药的雌激素组合物
US20070004693A1 (en) * 2005-06-16 2007-01-04 Warner Chilcott Company Inc. Estrogen compositions for vaginal administration
EP1898880A2 (en) * 2005-06-16 2008-03-19 Warner Chilcott Company Inc. Gel compositions for topical administration
ITMI20051790A1 (it) 2005-09-27 2007-03-28 3V Sigma Spa Addensanti policarbossilici facilmente bagnabili
US20070092457A1 (en) * 2005-10-24 2007-04-26 Librizzi Joseph J Compositions comprising polymeric emulsifiers and methods of using the same
US20070092458A1 (en) * 2005-10-24 2007-04-26 Librizzi Joseph J Compositions comprising polymeric emulsifiers and methods of using the same
TWI394789B (zh) 2005-12-22 2013-05-01 Nippon Catalytic Chem Ind 吸水性樹脂組成物及其製造方法、吸收性物品
EP1837348B9 (en) 2006-03-24 2020-01-08 Nippon Shokubai Co.,Ltd. Water-absorbing resin and method for manufacturing the same
CA2643608A1 (en) 2006-03-31 2007-10-11 Basf Se Process for preparing acrylate copolymers
ES2561839T3 (es) * 2006-11-09 2016-03-01 Lubrizol Advanced Materials, Inc. Polímeros que mitigan la irritación y sus usos
US7803403B2 (en) * 2006-11-09 2010-09-28 Johnson & Johnson Consumer Companies, Inc. Low-irritation compositions and methods of making the same
KR100844181B1 (ko) * 2007-02-15 2008-07-04 애경정밀화학 주식회사 카르복시기 함유 중합체 제조용 조성물 및 이를 이용하여제조된 중합체
US7820608B2 (en) * 2007-07-17 2010-10-26 Johnson & Johnson Consumer Companies, Inc. Methods of cleansing dyed hair
FR2922767B1 (fr) * 2007-10-24 2009-12-18 Seppic Sa Procede de preparation d'une composition vaccinale comprenant au moins un antigene et au moins un adjuvant.
CN102176822B (zh) * 2008-10-08 2013-12-04 詹森药业有限公司 含杀生物剂的高固体分散体
BRPI0922802B1 (pt) * 2008-11-21 2019-09-17 Hercules Incorporated Copolímero de ácido carboxílico reticulado
DE102009054532A1 (de) 2008-12-22 2010-07-01 Basf Se Verfahren zur Herstellung von Partikeln umfassend wasserlösliche Polymere
EP2415787A4 (en) * 2009-04-01 2013-11-27 Mitsui Chemicals Inc METHOD FOR PREVENTING ENCRAGEMENT IN CHEMICAL EQUIPMENT AND INHIBITOR OF ENCRASION
FR2950060B1 (fr) 2009-09-11 2011-10-28 Soc Dexploitation De Produits Pour Les Industries Chimiques Seppic Nouveau polymere en poudre, procede pour sa preparation et utilisation comme epaississant
EP2484439B1 (en) 2009-09-29 2022-12-14 Nippon Shokubai Co., Ltd. Particulate water absorbent and process for production thereof
KR101722805B1 (ko) 2009-11-26 2017-04-05 바스프 에스이 화장품 및 피부과용 제제에서의 초분지형 폴리에스테르의 용도
KR20120102725A (ko) 2009-11-26 2012-09-18 바스프 에스이 화장품 및 피부과용 제제에서의 초분지형 폴리카르보네이트의 용도
US20110123473A1 (en) * 2009-11-26 2011-05-26 Basf Se Use of highly-branched polycarbonates in cosmetic and dermatological formulations
WO2011081907A1 (en) 2009-12-14 2011-07-07 Lubrizol Advanced Materials, Inc. Cassia derivatives
KR20130019373A (ko) 2010-03-02 2013-02-26 바스프 에스이 음이온성의 회합성 레올로지 개질제
KR20130019374A (ko) 2010-03-02 2013-02-26 바스프 에스이 음이온성의 회합성 레올로지 개질제
US8673275B2 (en) 2010-03-02 2014-03-18 Basf Se Block copolymers and their use
KR20130036188A (ko) 2010-03-02 2013-04-11 바스프 에스이 블록 공중합체 및 이의 용도
JP5758987B2 (ja) 2010-04-29 2015-08-05 ルブリゾル アドバンスド マテリアルズ， インコーポレイテッド カシア誘導体
FR2961815B1 (fr) 2010-06-25 2013-05-10 Coatex Sas Emulsions acryliques alkali gonflables a l'acide acrylique, leur utilisation dans des formulations aqueuses et formulations les contenant.
CN103068865B (zh) 2010-07-09 2016-01-13 路博润高级材料公司 结构化的丙烯酸酯共聚物增稠剂
US9068148B2 (en) 2010-07-09 2015-06-30 Lubrizol Advanced Materials, Inc. Blends of acrylic copolymer thickeners
WO2012022668A1 (en) 2010-08-16 2012-02-23 Basf Se Anionic associative rheology modifiers
WO2012030750A2 (en) 2010-09-02 2012-03-08 Lubrizol Advanced Materials, Inc. Polymers and compositions
WO2012044929A2 (en) 2010-09-30 2012-04-05 Lubrizol Advanced Materials, Inc. Structured acrylate copolymer for use in multi-phase systems
WO2012047957A1 (en) 2010-10-05 2012-04-12 Lubrizol Advanced Materials, Inc. Acrylate copolymer thickeners
US20120184654A1 (en) * 2011-01-14 2012-07-19 Ashland Licensing And Intellectual Property Llc High viscosity spray emulsion concrete release agent
EP2717844B1 (en) 2011-06-10 2015-07-08 Lubrizol Advanced Materials, Inc. Cassia derivatives
ES2554952T3 (es) 2011-09-13 2015-12-28 Lubrizol Advanced Materials, Inc. Microgeles sensibles a tensioactivos
JP6165735B2 (ja) 2011-09-13 2017-07-19 ルブリゾル アドバンスド マテリアルズ， インコーポレイテッド 界面活性剤応答性分散重合ミクロゲル
US9243142B2 (en) 2011-11-16 2016-01-26 Momentive Performance Materials Inc. Association product of amino functional hydrophobic polymers with hydrophilic polymers containing acid groups, methods of preparation, and applications for employing the same
FR2983721B1 (fr) 2011-12-08 2014-05-09 Seppic Sa Nouvelles emulsions huile-dans-eau riches en sels, a viscosite elevee et stables au cours du temps
FR2983722B1 (fr) 2011-12-08 2014-06-27 Seppic Sa Nouvelles emulsions huile-dans-eau riches en sels, stabilisees avec des gommes naturelles, a viscosite elevee et stables au cours du temps.
CN104105714B (zh) 2011-12-21 2017-04-05 路博润高级材料公司 制备丙烯酸聚合物的方法以及由此制得的产物
FR2986004B1 (fr) 2012-01-25 2014-03-14 Seppic Sa Nouveau polymere epaississant reduisant le caractere collant des formules cosmetiques a base de glycerine
EP2809765A1 (en) 2012-01-30 2014-12-10 Reckitt Benckiser LLC Stable, viscous, peroxide containing lavatory treatment compositions
FR2987361B1 (fr) * 2012-02-29 2014-07-18 Soc Dexploitation De Produits Pour Les Industries Chimiques Seppic Nouveau polymere d'acrylate de silicone et de methacrylate de trifluoro-ethyle, preparation et utilisation en cosmetique
ES2592564T3 (es) 2012-06-15 2016-11-30 Lubrizol Advanced Materials, Inc. Espesantes micelares a base de alquilglucósido para sistemas tensioactivos
CA2876125A1 (en) * 2012-06-19 2013-12-27 Watever Inc. Coating composition
FR2992323B1 (fr) 2012-06-25 2015-07-03 Soc Dexploitation De Produits Pour Les Industries Chimiques Seppic Nouveau latex inverse auto-inversible exempt de tensioactif, son utilisation comme agent epaississant dans une composition cosmetique
EP2732832A3 (en) 2012-11-14 2015-07-01 Universitair Medisch Centrum Groningen (UMCG) Drug delivery device comprising an active compound and a thermo-sensitive polymeric material
US9707162B2 (en) 2012-11-30 2017-07-18 Reckitt & Colman (Overseas) Limited Microbicidal personal care compositions comprising metal ions
EP2934679B1 (en) 2012-12-20 2017-10-11 Lubrizol Advanced Materials, Inc. Irritation mitigating polymers and uses therefor
MX357773B (es) 2013-02-06 2018-07-24 Lubrizol Advanced Mat Inc Composicion y metodo para alaciado de cabello semi-permanente.
KR20150128792A (ko) 2013-03-08 2015-11-18 루브리졸 어드밴스드 머티어리얼스, 인코포레이티드 케라틴성 기재로부터 실리콘 침적의 손실을 완화시키는 폴리머 및 방법
WO2014138327A1 (en) 2013-03-08 2014-09-12 Lubrizol Advanced Materials, Inc. Improved foaming performance in cleansing compositions through the use of nonionic, amphiphilic polymers
JP6234543B2 (ja) * 2013-03-14 2017-11-22 ナノシス・インク． ナノ結晶用のアルキル−酸リガンド
FR3008981B1 (fr) 2013-07-24 2016-11-18 Soc Dexploitation De Produits Pour Les Industries Chimiques Seppic Nouveau polymere en poudre, procede pour sa preparation et utilisation comme epaississant
WO2015042013A1 (en) 2013-09-18 2015-03-26 Lubrizol Advanced Materials, Inc. Stable linear polymers
CN103483491A (zh) * 2013-09-29 2014-01-01 清远市威仕泽科技孵化器有限公司 一种卡波姆及其制备方法
WO2015059084A1 (de) 2013-10-21 2015-04-30 Basf Se Fällungspolymerisation in gegenwart eines tertiären amins und eines anhydrids
EP3065831A1 (en) 2013-11-08 2016-09-14 Lubrizol Advanced Materials, Inc. Semi-permanent hair straightening composition and method
EP2907828A1 (de) 2014-02-14 2015-08-19 Basf Se Verfahren zur Herstellung von kationogen-ampholytischen VP/VI-Copolymeren
CA2939606A1 (en) 2014-02-21 2015-08-27 Lubrizol Oilfield Solutions, Inc. Synthetic hydratable polymers for use in fracturing fluids and methods for making and using same
WO2016178660A1 (en) 2014-05-02 2016-11-10 Hercules Inncorporated Personal care composition for a keratin substrate comprising conditioning and/or styling polymer
KR20170003955A (ko) 2014-05-05 2017-01-10 루브리졸 어드밴스드 머티어리얼스, 인코포레이티드 균질한 필름 조성물
JP6873897B2 (ja) 2014-07-09 2021-05-19 ルブリゾル アドバンスド マテリアルズ， インコーポレイテッド ヒドロゲル組成物
CN107614264B (zh) 2014-12-05 2020-02-04 佛罗里达大学研究基金会有限公司 使用相变材料作为支撑体的3d打印
WO2016130953A1 (en) 2015-02-13 2016-08-18 University Of Florida Research Foundation, Inc. High speed 3d printing system for wound and tissue replacement
US11390835B2 (en) 2015-05-08 2022-07-19 University Of Florida Research Foundation, Inc. Growth media for three-dimensional cell culture
ES2759984T3 (es) 2015-06-17 2020-05-12 Clariant Int Ltd Procedimiento para la producción de polímeros a base de laurato de acriloildimetilo, monómeros neutros, monómeros con ácidos carbónicos y reticulantes especiales
BR112017023714A2 (pt) 2015-06-17 2018-07-17 Clariant International Ltd. processo para preparação de polímeros à base de dimetiltaurato de acriloíla e monômeros neutros
EP3106471A1 (de) 2015-06-17 2016-12-21 Clariant International Ltd Verfahren zur herstellung von polymeren auf basis von acryloyldimethyltaurat, neutralen monomeren und speziellen vernetzern
EP3106470A1 (de) 2015-06-17 2016-12-21 Clariant International Ltd Verfahren zur herstellung von polymeren auf basis von acryloyldimethyltaurat und speziellen vernetzern
EP3310734B1 (de) 2015-06-17 2019-02-06 Clariant International Ltd Verfahren zur herstellung von polymeren auf basis von acryloyldimethyltaurat, neutralen monomeren und monomeren mit carboxylatgruppen
US11027483B2 (en) 2015-09-03 2021-06-08 University Of Florida Research Foundation, Inc. Valve incorporating temporary phase change material
EP3371238A1 (en) 2015-11-05 2018-09-12 Lubrizol Advanced Materials, Inc. Thermoformable dual network hydrogel compositions
WO2017096263A1 (en) 2015-12-04 2017-06-08 University Of Florida Research Foundation, Incorporated Crosslinkable or functionalizable polymers for 3d printing of soft materials
US20190142727A1 (en) * 2016-03-31 2019-05-16 Sumitomo Seika Chemicals Co., Ltd. Gel composition, cosmetic and manufacturing method for gel composition
FR3054793B1 (fr) 2016-08-05 2018-07-27 Soc Dexploitation De Produits Pour Les Industries Chimiques Seppic Composition limpide epaissie, riche en sels, procede pour son eclaircissement et utilisation en cosmetique
FR3054791B1 (fr) 2016-08-05 2018-07-27 Societe D'exploitation De Produits Pour Les Industries Chimiques Seppic Serum cosmetique limpide epaissi et riche en sels, procede pour eclaircir un hydrogel et utilisation en cosmetique
US11124644B2 (en) 2016-09-01 2021-09-21 University Of Florida Research Foundation, Inc. Organic microgel system for 3D printing of silicone structures
DE102016225147A1 (de) 2016-12-15 2018-06-21 Clariant International Ltd Hybrid-Polymere und die Verwendung als Additive bei Tiefbohrungen
DE102016225151A1 (de) 2016-12-15 2018-06-21 Clariant International Ltd Hybrid-Polymere und die Verwendung als Additive bei Tiefbohrungen
US20200069533A1 (en) 2017-03-23 2020-03-05 Lubrizol Advanced Materials, Inc. Denture adhesives
US20200375890A1 (en) 2017-03-23 2020-12-03 Particle Sciences, Inc. Implantable and removable drug delivery device
WO2018204317A1 (en) 2017-05-02 2018-11-08 Lubrizol Advanced Materials, Inc. Improved extended release highly loaded drug compositions
JP7202305B2 (ja) * 2017-08-30 2023-01-11 住友精化株式会社 カルボキシル基含有重合体組成物及びその製造方法
WO2019094668A1 (en) 2017-11-10 2019-05-16 Lubrizol Advanced Materials, Inc. Process for preparing and compositions of macrosphere formulations
WO2019126162A1 (en) 2017-12-20 2019-06-27 Lubrizol Advanced Materials, Inc. Cleansing composition containing oil with foaming properties
US11680241B2 (en) 2018-02-08 2023-06-20 University Of Florida Research Foundation, Inc. Perfusion enabled bioreactors
US20210038494A1 (en) 2018-03-16 2021-02-11 Lubrizol Advanced Materials, Inc. Foaming cleanser compositions containing a non-polar oil and amphiphilic polymer
MX2020010776A (es) 2018-04-12 2022-08-15 Lubrizol Advanced Mat Inc Composición y método para la modificación del cabello.
WO2020028672A1 (en) 2018-08-01 2020-02-06 University Of Florida Research Foundation Perfusion bioreactor driven by osmotic pressure gradients
EP3610853A1 (en) 2018-08-15 2020-02-19 The Boots Company PLC Cosmetic compositions
WO2020106662A1 (en) 2018-11-20 2020-05-28 The Lubrizol Corporation Graphene production and composition
WO2020123609A1 (en) 2018-12-11 2020-06-18 Lubrizol Advanced Materials, Inc. Compositions and treatment methods for the mitigation of winter season related pruritus
JP2022531904A (ja) 2019-05-09 2022-07-12 ビーエーエスエフ ソシエタス・ヨーロピア パーソナル洗浄組成物及び改善されたコンディショニングの利益を達成する方法
FR3106979B1 (fr) 2020-02-12 2022-07-22 Soc Dexploitation De Produits Pour Les Industries Chimiques Seppic Composition à usage topique se présentant sous la forme d’un gel comprenant une eau de minéralisation
FR3107454B1 (fr) 2020-02-20 2023-02-10 Soc Dexploitation De Produits Pour Les Industries Chimiques Seppic Adjuvant de vaccin comprenant un microlatex inverse
FR3112473A1 (fr) 2020-07-15 2022-01-21 Societe D'exploitation De Produits Pour Les Industries Chimiques Seppic Composition hydro-alcoolique pour la désinfection des mains
CN117015565A (zh) 2021-03-05 2023-11-07 路博润先进材料公司 用于润湿和分散丙烯酸聚合物的方法
WO2022245758A1 (en) 2021-05-17 2022-11-24 Lubrizol Advanced Materials, Inc. Hair color compositions for mitigating color loss
CN117881408A (zh) 2021-09-03 2024-04-12 路博润先进材料公司 折扇叶属物种提取物用于促进毛发生长的用途
WO2023060083A1 (en) 2021-10-05 2023-04-13 University Of Florida Research Foundation Compositions, systems, and methods relating to three-dimensional (3d) bioprinted liver tissue models
WO2023191852A1 (en) 2022-03-28 2023-10-05 Lubrizol Advanced Materials, Inc. Stable dentifrice compositions with high sodium bicarbonate loading

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4529773A (en) † 1982-03-17 1985-07-16 David Witiak Alkali-soluble emulsion polymers in acidic surfactant compositions
EP0151467A2 (de) † 1984-02-09 1985-08-14 Hoechst Aktiengesellschaft Wässrige Funktionsflüssigkeiten auf der Basis von Polymeren
EP0172025A2 (en) † 1984-08-15 1986-02-19 Ciba Specialty Chemicals Water Treatments Limited Polymeric compositions
EP0333499A1 (en) † 1988-03-18 1989-09-20 Ciba Specialty Chemicals Water Treatments Limited Polymerisation processes and products obtained from these
US4892916A (en) † 1984-08-15 1990-01-09 Allied Colloids Limited Polymeric thickeners and their production

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2270268B1 (zh) * 1974-05-07 1978-04-21 Anvar
US4180619A (en) * 1975-03-19 1979-12-25 Ppg Industries, Inc. Crosslinked acrylic polymer microparticles
DE2862369D1 (en) * 1977-07-12 1984-03-08 Ici Plc Linear or branched ester-ether block copolymers and their use as surfactants either alone or in blends with conventional surfactants
US4310698A (en) * 1978-10-20 1982-01-12 Ciba-Geigy Corporation Fluorochemical non-ionic surfactants
US4375533A (en) * 1981-07-08 1983-03-01 The Bf Goodrich Company Polymerization process for carboxyl containing polymers
US4420596A (en) * 1982-09-27 1983-12-13 The B. F. Goodrich Company Process for polymerizing unsaturated acids in mineral spirits
US4419502A (en) * 1982-09-29 1983-12-06 The B. F. Goodrich Company Polymerization process for carboxyl containing polymers
US4526937A (en) * 1983-08-31 1985-07-02 The B. F. Goodrich Company Polycarbonates having plasticizers with fugitive activity
KR920003081B1 (ko) * 1984-06-29 1992-04-13 더 다우 케미칼 캄파니 에틸렌과 불포화 카복실산의 인터폴리머의 제조방법
JPH0617373B2 (ja) * 1984-07-06 1994-03-09 株式会社リコー 粒子径分布の狭い重合体粒子の製造法
US4594200A (en) * 1984-11-15 1986-06-10 Halliburton Company Compositions for increasing hydrocarbon production from subterranean formations
US4911736A (en) * 1985-09-18 1990-03-27 The Standard Oil Company Emulsifier and stabilizer for water base emulsions and dispersions of hydrocarbonaceous materials
US4692502A (en) * 1986-06-09 1987-09-08 The Standard Oil Company Polymerization process for carboxyl containing polymers utilizing oil soluble ionic surface active agents
GB9013722D0 (en) * 1990-06-20 1990-08-08 Shell Int Research Interpolymer dispersions from vinyl esters of branched chain carboxylic acids and ethylenically unsaturated acids and/or their esters

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4529773A (en) † 1982-03-17 1985-07-16 David Witiak Alkali-soluble emulsion polymers in acidic surfactant compositions
EP0151467A2 (de) † 1984-02-09 1985-08-14 Hoechst Aktiengesellschaft Wässrige Funktionsflüssigkeiten auf der Basis von Polymeren
EP0172025A2 (en) † 1984-08-15 1986-02-19 Ciba Specialty Chemicals Water Treatments Limited Polymeric compositions
US4892916A (en) † 1984-08-15 1990-01-09 Allied Colloids Limited Polymeric thickeners and their production
EP0333499A1 (en) † 1988-03-18 1989-09-20 Ciba Specialty Chemicals Water Treatments Limited Polymerisation processes and products obtained from these

Also Published As

Publication number Publication date
MX183685B (es) 1997-01-08
US5468797A (en) 1995-11-21
AU4438893A (en) 1994-03-03
CA2104835A1 (en) 1994-02-27
CN1085571A (zh) 1994-04-20
KR100294936B1 (ko) 2001-09-17
ES2111673T5 (es) 2008-11-01
TW260676B (en) 1995-10-21
DE69315910D1 (de) 1998-02-05
DE69315910T2 (de) 1998-06-10
ATE161553T1 (de) 1998-01-15
US5288814A (en) 1994-02-22
ES2111673T3 (es) 1998-03-16
IL106724A (en) 1996-10-16
KR940003976A (ko) 1994-03-14
JPH06199969A (ja) 1994-07-19
BR9303434A (pt) 1994-03-15
MY132334A (en) 2007-10-31
AU676841B2 (en) 1997-03-27
MX9305127A (es) 1994-05-31
EP0584771A1 (en) 1994-03-02
EP0584771B1 (en) 1997-12-29
US5349030A (en) 1994-09-20
CN1051094C (zh) 2000-04-05
ZA936157B (en) 1994-03-17
MY110032A (en) 1997-11-29
IL106724A0 (en) 1993-12-08
US5373044A (en) 1994-12-13
JP3273089B2 (ja) 2002-04-08

Similar Documents

Publication Publication Date Title
EP0584771B2 (en) Easy to disperse polycarboxylic acid thickeners
CA1250081A (en) Preparation of carboxyl-containing polymers
US4420596A (en) Process for polymerizing unsaturated acids in mineral spirits
EP0069371B2 (en) Improved polymerization process for carboxyl containing polymers
US5506315A (en) Preparation of copolymers of monoethylenically unsaturated monomers containing acid groups and N-vinyllactams
EP0128237B1 (en) Improved water thickening agents
CA1267483A (en) Process for the production of a water-soluble polymer dispersion
EP0608845B1 (en) Multifunctional maleate polymers
US4419502A (en) Polymerization process for carboxyl containing polymers
US4539362A (en) Polymerization process
JPS6012361B2 (ja) 共重合体の製造方法
US4692502A (en) Polymerization process for carboxyl containing polymers utilizing oil soluble ionic surface active agents
US4587290A (en) Polymerization process using nonionic surfactant and copolymerizable unsaturated polyethylene glycol
EP0838498B1 (en) Carboxylated polymer composition
FI73228C (fi) Foerfarande foer framstaellning av en steriskt stabiliserad vattenhaltig polymerdispersion.
EP2403884B1 (en) Non-hydrocarbyl hydrophobically modified polycarboxylic polymers
EP0005363A1 (en) Process for the preparation of carboxyl-containing polymers in an anionic form in the dry state; interpolymers thus obtained
JPH0516447B2 (zh)
US4701494A (en) Process for the preparation of water-soluble vinyl saccharide polymers

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

17P Request for examination filed

Effective date: 19940810

17Q First examination report despatched

Effective date: 19960118

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19971229

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19971229

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19971229

Ref country code: CH

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19971229

REF Corresponds to:

Ref document number: 161553

Country of ref document: AT

Date of ref document: 19980115

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 69315910

Country of ref document: DE

Date of ref document: 19980205

ET Fr: translation filed
ITF It: translation for a ep patent filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2111673

Country of ref document: ES

Kind code of ref document: T3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19980329

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980824

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

26 Opposition filed

Opponent name: BASF AKTIENGESELLSCHAFT, LUDWIGSHAFEN

Effective date: 19980924

NLR1 Nl: opposition has been filed with the epo

Opponent name: BASF AKTIENGESELLSCHAFT, LUDWIGSHAFEN

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBO Opposition rejected

Free format text: ORIGINAL CODE: EPIDOS REJO

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

APAE Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOS REFNO

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: NOVEON IP HOLDINGS CORP.

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

NLS Nl: assignments of ep-patents

Owner name: NOVEON IP HOLDINGS CORP.

NLT2 Nl: modifications (of names), taken from the european patent patent bulletin

Owner name: NOVEON IP HOLDINGS CORP.

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

Ref country code: FR

Ref legal event code: CD

BECA Be: change of holder's address

Free format text: 20020221 *NOVEON IP HOLDINGS CORP.:9911 BRECKSVILLE ROAD, CLEVELAND, OHIO 44141-3247

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20050803

Year of fee payment: 13

APBU Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9O

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060824

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20060824

Year of fee payment: 14

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: NOVEON, INC.

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

NLT2 Nl: modifications (of names), taken from the european patent patent bulletin

Owner name: NOVEON, INC.

Effective date: 20060920

NLS Nl: assignments of ep-patents

Owner name: NOVEON, INC.

Effective date: 20060901

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

BECN Be: change of holder's name

Owner name: *LUBRIZOL ADVANCED MATERIALS INC.

Effective date: 20061005

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080301

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20080301

27A Patent maintained in amended form

Effective date: 20080507

AK Designated contracting states

Kind code of ref document: B2

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

REG Reference to a national code

Ref country code: ES

Ref legal event code: PC2A

REG Reference to a national code

Ref country code: ES

Ref legal event code: DC2A

Date of ref document: 20080724

Kind code of ref document: T5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20090915

Year of fee payment: 17

BERE Be: lapsed

Owner name: *LUBRIZOL ADVANCED MATERIALS INC.

Effective date: 20100831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100831

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20120828

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20120823

Year of fee payment: 20

Ref country code: FR

Payment date: 20120830

Year of fee payment: 20

Ref country code: ES

Payment date: 20120827

Year of fee payment: 20

Ref country code: DE

Payment date: 20120829

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 69315910

Country of ref document: DE

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20130823

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20130827

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20130823

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20140925

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20130825